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Red Blood Cells Polarize Green Laser Light Revealing Hemoglobin′s Enhanced Non‐Fundamental Raman Modes 下载免费PDF全文
Dr. Katarzyna M. Marzec Dr. David Perez‐Guaita Dr. Marleen de Veij Prof. Don McNaughton Prof. Malgorzata Baranska Dr. Matthew W. A. Dixon Prof. Leann Tilley Prof. Bayden R. Wood 《Chemphyschem》2014,15(18):3963-3968
In general, the first overtone modes produce weak bands that appear at approximately twice the wavenumber value of the fundamental transitions in vibrational spectra. Here, we report the existence of a series of enhanced non‐fundamental bands in resonance Raman (RR) spectra recorded for hemoglobin (Hb) inside the highly concentrated heme environment of the red blood cell (RBC) by exciting with a 514.5 nm laser line. Such bands are most intense when detecting parallel‐polarized light. The enhancement is explained through excitonic theory invoking a type C scattering mechanism and bands have been assigned to overtone and combination bands based on symmetry arguments and polarization measurements. By using malaria diagnosis as an example, we demonstrate that combining the non‐fundamental and fundamental regions of the RR spectrum improves the sensitivity and diagnostic capability of the technique. The discovery will have considerable implications for the ongoing development of Raman spectroscopy for blood disease diagnoses and monitoring heme perturbation in response to environmental stimuli. 相似文献
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Mechler M Kukhlevsky SV Mechler A McNaughton D 《Physical chemistry chemical physics : PCCP》2011,13(46):20772-20778
Optical field distribution in micro-nano geometries of miniaturized optical devices is often significantly different from that in identical but macroscopic geometries. Plasmon effects and near-field diffraction can enhance the local field intensity, leading to enhanced cross section for light absorption and scattering, which can be utilized in substrate-enhanced spectroscopies for the detection of trace amounts of adsorbed chemicals. A specific problem is an ingenious but only empirically described way to enhance signal intensity in Raman spectroscopy by the use of a substrate patterned with gold coated micron size pyramidal pits. While Raman enhancement on nanostructured substrates is generally attributed to surface plasmons, here the micron size, and thus the sub-wavelength to near-wavelength dimensions suggest that resonant enhancement emanating from optical near-field diffraction might also play a role. To answer this question, light diffraction in a projection of the pyramidal pit: a V-groove, was modelled with a modified Neerhoff-Mur formalism suitable to calculate electromagnetic field distribution in sub-wavelength structures. Under the boundary conditions a perfect conductor screen was assumed, which excludes plasmon effects. The calculations show that interference in the cavity causes a modest resonant increase in local intensity and that near-field diffraction strongly influences the field distribution, which is explained with the electrodynamic edge effect. The magnitude of the resonant electric field on its own cannot account for the experimentally observed Raman enhancement. However, a resonant enhancement of a similar magnitude is expected for the emitted Stokes frequencies. In this case the geometry implements the conditions for the classical electromagnetic Raman enhancement, ~E(4), in a good agreement with experimental results. 相似文献
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Sinn I Kinnunen P Albertson T McNaughton BH Newton DW Burns MA Kopelman R 《Lab on a chip》2011,11(15):2604-2611
Inappropriate antibiotic use is a major factor contributing to the emergence and spread of antimicrobial resistance. The long turnaround time (over 24 hours) required for clinical antimicrobial susceptibility testing (AST) often results in patients being prescribed empiric therapies, which may be inadequate, inappropriate, or overly broad-spectrum. A reduction in the AST time may enable more appropriate therapies to be prescribed earlier. Here we report on a new diagnostic asynchronous magnetic bead rotation (AMBR) biosensor droplet microfluidic platform that enables single cell and small cell population growth measurements for applications aimed at rapid AST. We demonstrate the ability to rapidly measure bacterial growth, susceptibility, and the minimum inhibitory concentration (MIC) of a small uropathogenic Escherichia coli population that was confined in microfluidic droplets and exposed to concentrations above and below the MIC of gentamicin. Growth was observed below the MIC, and no growth was observed above the MIC. A 52% change in the sensor signal (i.e. rotational period) was observed within 15 minutes, thus allowing AST measurements to be performed potentially within minutes. 相似文献
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Jiang H Appadoo D Robertson E McNaughton D 《Journal of computational chemistry》2002,23(13):1220-1225
The vibrational assignments of difluoromethane, cis and trans 1,2-difluoroethylene, trifluoroethylene, 2-fluoropropene, 1,1-difluoroethylene, and tetrafluoroethylene have been reassessed in the light of recent theoretical work. Inconsistent experimental wave number values and assignments have been clarified, and some changes to the experimental assignments are proposed. The assignments compare favorably with recent scaled density functional theory calculations using the hybrid three-parameter B3-PW91 density functional. 相似文献
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Enthalpies of the decomposition reactions MX2L2(c)→MX2(c) + 2L (g), where M is Mn, Co, Ni, Cu, or Cd, X is Cl and/or Br, and L is benzothiazole or 2-methyl-benzothiazole have been measured by use of a differential scanning calorimeter. Specific heats and enthalpies of sublimation of some of the complexes have been obtained. 相似文献
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In this paper we develop numerical algorithms for the continuationof degenerate homoclinic connections in planar systems. We considerthe case where the equilibrium point has zero trace and twocases of higher-order degeneracies. The method we propose isable to continue homoclinic connections of order up to codimension-four.Application of the algorithm to four examples supports its validityand demonstrates its usefulness. 相似文献